Derivatives of fluorinated ketones and process for producing same



United States Patent O 3,324,185 DERIVATIVES F FLUORINATED KETONES AND PROCESS FOR PRODUCING SAME Everett E. Gilbert and Morton Litt, Morris Township, Morris County, and Julian A. (ltto, Stockholm, N.J., assignors to Allied Chemical Corporation, New York, N.Y.. a corporation of New York No Drawing. Filed Dec. 2, 1963, Ser. No. 327,520 7 Claims. (Cl. 260-609) This invention relates to derivatives of fiuorinated ketones useful as active pesticidal toxicants.

It is known that phenol may be reacted with hexafiuoroacetone in the presence of anhydrous hydrogen fluoride. The phenol and hexafluoroacetone react only at 2:1 mol ratio in accordance with the following equation:

wherein R is a nuclearly hydroxy-substituted aryl radical which is connected to the adjacent carbon atom by an ortho-linkage and X and Y are members selected from the group consisting of fluorine and chlorine.

These ortho-derivatives, as well as para-derivatives, of fluorinated ketones may be readily prepared by reacting a nuclearly hydroxy-substituted aromatic compound having the general formula:

ROH

wherein R is an aryl radical having at least one of a free orthoand a free para-position with a hexahaloacetone compound having the general formula:

(CF X) (CF Y) CO wherein X and Y are members selected from the group consisting of fluorine and chlorine under non-catalytic conditions or in the presence of a sulfonic acid catalyst. The aromatic compound and 'hexahaloacetone compound react only at 1:1 mol ratio, as illustrated by the following equation wherein the aromatic compound is phenol and the hexahaloacetone compound is hexafluoroacetone:

C(O a)2 (CFmC 0 If the aromatic compound employed in the above reaction contains a free ortho-position, as in the case of phenol, substitution occurs in that position. If, however, the ortho-positions are occupied, substitution occurs in the para-position.

The hexahaloacetone compounds which may be utilized in the present invention include hexafluoroacetone, pentafluoromonochloroacetone and sym tetrafluorodichloroacetone.

The nuclearly hydroxy-substituted aromatic compounds which are preferred in the process of this invention are compounds selected from the group consisting of phenol and alkyl-substituted, cycloalkylsubstituted, alkyhnercapto-substituted and aryl-substituted phenols containing at least one of a free orthoand a free paraposition. The alkyl groups of these compounds preferably contain from 1 to 9 carbon atoms. Typical examples of the compounds are phenol, 4-cresol, 2,6-dimethylphenol, 2,6-di-tert.-butylphenol, 3-cresol, 2- cresol, 2-tert.-butylphenol, 4-cyclohexylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylp'henol, 2,6-diisopropylphenol, 2-methyl-6-tert.-butylphenol, 4-nonylphenol, 2-cyclohexylphenol, Z-phenylpjhenol, 4-phentylphenol and 4-methylmercaptophenol. Other suitable aromatic compounds include 2-chlorophenol, 4-chlorophenol, l-naphthol, resorcinol, 1,5-naphthalenediol and Bisphenol-A (p,p'-isopropylidenediphenol) The reactants are generally employed in mol ratio of about 0.75-1.5 mols of aromatic compound per mol of ketone, preferably about 1.0-1.2 mols of aromatic compound per mol of ketone. 1f the reaction is carried out employing lower or higher mol ratios, significant contamination of the desired product may occur.

The reaction may be carried out in the absence of a catalyst or preferably in the presence of a sulfonic acid catalyst. Use of a sulfonic acid catalyst enables the reaction to proceed at a considerably faster rate.

The sulfonic acid catalyst may be employed in three forms: (1) as an alkyl or aryl sulfonic acid per se, (2) as a sulfonic acid formed by adding sulfuric acid to the nuclearly hydroxy-susbtituted aromatic compound, and (3) as a sulfonic acid form ion-exchange resin such as Dowex 50 (a sulfonated styrene-divinyl benzene copolymer having a total exchange capacity ranging from 0.3 to 2.3). Illustrative examples of alkyl sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, methanedisulfonic acid, methanetrisulfonic acid and sulfochloroacetic acid. Aryl sulfonic acids are illustrated by benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, chlorobenzenesulfonic acid, naphthalenesulfonic acids, dodecylbenzenesulfonic acid and petroleum sulfonic acids.

The catalyst is employed in amount ranging from about 0.1 to 10% by Weight based on the amount of aromatic compound charged. For economical operation and minimum waste the sulfonic acid catalyst is employed in amount of about 2 to 5% by Weight based on the aromatic compound charged.

The reaction temperature may vary between about 0 and 350 C., and is preferably about 50 to about C. Of course, if super-atmospheric or sub-atmospheric pressures are employed, higher and lower temperatures may be used.

In preferred operation, a solvent is employed which is inert under the conditions of reaction and is a solvent for the reactants. Suitable solvents include benzene and its alkylated and halogenated derivatives such as xylene and chlorobenzene. The amount of solvent is not critical and may vary in amount from about 0.5 to 10 parts, and preferably about 1 to 5 parts, per part of aromatic compound charged.

Recovery of the derivatives of fluorinated ketones from the reaction mixture may be accomplished by conventional means. For example, the solvent may be readily removed by distillation to leave product as residue or the product may be precipitated by cooling and filtered off.

The derivatives of fluorinated ketones have been found to possess outstanding pesticidal, including herbicidal and/or insecticidal and miticidal, activity.

The present invention is further illustrated by the examples set forth below, in which parts are by weight.

3 Example 1 27 parts of 4-cresol and 100 parts of xylene were placed in a reaction vessel equipped with a mechanical stirrer, heater and Dry Ice-acetone reflux condenser. The vessel was swept with dry nitrogen to remove any pos- Examples 3 to Various phenolic compounds were reacted with hexafluoroacetone using the procedure described in Example 2. The results of these examples, as well as additional 5 data on Examples 1 and 2, are given in Table I set forth sible moisture and was then heated to 100 C. below.

TABLE I Analysis of Product Phenolic Rene. Melting Yield, Ex. Compound Time, Product Carbon Hydrogen Fluorine P001619, Percent Hrs.

Cale. Found Cale. Found Cale. Found 1 4-cresol 14 2-(1,1,1,3,3,3-hcxafiuoro-2-hydroxy- 121-0 isopropyl)-4-methylpheno1. 2 do 7% 2-(1,1,1,3,3-hexailuoro-2-hydroxyiso- 43.7 43.1 2.9 3.3 41.5 42.0 121-6 propyl)-4-rnethylphenol. 3 Phenol 32 2-(1,1,1,3,3,3-hexailuoro-2-hydroxy- 41.5 41.5 2.3 2.3 43.8 44.0 72-5 35 isopropyl) phenol. 4 2,6-din1ethyl- 28 4-(1,1,1,3,3,3-hexailuoro-2-hydroxy- 45.8 44.8 3.5 3.6 39.5 38.0 93-194 85 phenol. isopropyl)-2,6-dimethylphcnol. 5 2-tert.-l)utyl- 10 6-(1,1,1,3,3,3-hexafluoro-2-hydroxy- 49.3 49.2 4.4 4.9 36.0 35.5 63-71 52 phenol. isopropyl)-2-tert.-butylphenol.

1 The product was proved to be the 2-derivative by its hydrolysis to cresotic acid. 1 The product was proved to be the 2-derivative by its hydrolysis to salicylic acld. Hexafluoroacetone was slowly admitted to the vessel un- 25 Example 6 til refluxing of it from the condenser caused the reaction temperature to drop. More hexafluoroacetone was added when the original temperature was again attained. parts of hexafiuoroacetone were added over a period of 40 hours. Heating was continued for 3 hours at 100 C. The reaction mixture was then washed with water, and the xylene was removed by distillation. The residue, upon recrystallization from hexane, melted at 121126 C. and comprised 20.5 parts of 2-(1,1,l,3,3,3-hexafluoro- 2-hydroxyisopropyl)-4-methylphenol.

Example 2 The process of Example 1 was repeated except that 2 parts of 4-toluenesulfonic acid were added. After a reaction period of 7 /2 hours, 23.5 parts of product was obtained. Infrared spectral comparison and mixed melting point showed it was identical with the product of Example 1.

94 parts of phenol and 5 parts of 4-toluenesulfonic acid catalyst were heated in a reaction vessel equipped with a mechanical stirrer, heater and reflux condenser. Sym-tetrafluorodichloroacetone was added slowly so that the reaction mixture was maintained at 110-130 C. 200 parts of the ketone were added over a 33-hour period. The resulting reaction mixture was poured into a container where it began to solidify upon cooling. It was taken up in 596 parts of chloroform, and an equal volume of hexane was then added to precipitate product. The precipitate was filtered off and dried to give 200 parts of 2 (1,3 dichloro l,1,3,3 tetrafluoro 2 hydroxyisopropyl) phenol.

Examples 7 to 15 tional data on Example 6, are set forth in Table 11 below.

TABLE II Analysis of Product Phenolic Rene. Melting Yield, Ex. Compound TiiIme, Product Carbon Hydrogen Chlorine P oint, Percent rs. C.

Cale. Found Cale. Found Calc. Found 6 Phenol 33 2-(1,3-dichlo1'o-1,1,3,3-tetrafiuoro-2- 36.8 36.8 2.1 2.2 24.2 24.0 128-33 68 hydroxyisopropyl) phenol. 7 2-cresol 10 6-(1,3-dichloro-1,1,3.3-tetrafiuoro-2- 39.0 39.0 2.6 2.9 23.1 22.8 128-30 58 hydi'oxyisopropyl)-2-rnctl1ylphenol. 8 2,6-din1ethyl- 4(1,3-dich10ro-1,1,3,3-tetrafluoro-2- 22.1 22. 7 38 phenol. hydroxyisopropyl)-2,6-din1ethylphenol. 9 4-cyelohexyl- 5 2-(1,3-diehloro1,1,3,3-tetrafiuoro-2- 18.9 18.4 202 70 phenol. hydroxyisopropyl)-4-eyc1ohexylphenol. 10 3-isopropyl- 5 2-(1,3-diehloro-1,1,3,3-tetrafiuoro-2- 21.2 20.0 55-03 66 phenol. hxydroixyisopropyl)-3-is0propylp 10110 11 2,6-diisopro- 40 4(1,3-dichloro-1,1,3,3-tetrafiuoro-2- 47. 7 48.2 5.0 4. 5 18.8 18. 5 88 pylpheuol. hfdroiryisopropyb-l6-dimetl1ylp ieno 12 2-te1t.butyl- 6 6-(1,3-dich1oro-1,1,3,3-tetrafiuoro-2- 20.3 19.9 144-9 30 phenol. hydroxyisopropyl)-2-tert.-buty1- phenol. -43 13 Z-methyl-G- 7 4-(1,3-dichloro-1,1,3,3-tet1'afluoro-2- 46.3 47.0 4.4 4.2 19.5 19.1 79

tert.-buty1- hydroxyisopropyl)-2-methyl-6- phenol. tert.-butylphenol. 14 l-naphthoL... 3 2-(1,3-dichloro-1,1,3,3-tetrafiuoro-2- 20.6 19.6 90-4 51 hydroxyisopropyl)-1-naphthol. 15 1,5-naphtha- 22 2-(1,3-dichloro-l,1,3,3-tetrafiuo1'o-2- 25.4 24. 6 276 88 lenediol. liydr'loxlyisopropyl)-1,5-naphthn one 10 1 The product was proved to be the 2-derivativc by its hydrolysis to salicylic acid.

,5 Other representative examples are given below.

Example 16 72 parts of l-naphthol, 100 parts of toluene and 2 parts of methanesulfonic acid were placed in a reaction vessel equipped with a mechanical stirrer, heater and Dry Ice-acetone reflux condenser, and the mixture was heated at 100C. (:10). 80 parts of hexafluoroacetone were slowly introduced over a 3-hour period. The reaction mixture was heated for one hour at reflux. The mixture was then cooled in Dry Ice, and solid was filtered off and washed with cold toluene and hexane. After recrystallization, 92 parts (59% yield) of 2-(1, 1,1,3,3,3-hexafluoro-2- hydroxyisopropyD-l naphthol were obtained.

Fluorine analysis of the product gave 34.9% (theory, 33.6%

Example 17 The product analyzed as follows:

Fluorine Chlorine Calculated, percent- 23. 2 32. Found, percent 23. 5 32. 5

Example 18 27 parts of 3-cresol, 100 parts of xylene and 1 part of concentrated sulfuric acid are placed in a reaction vessel equipped with a mechanical stirrer, heater and Dry Iceacetone reflux condenser, and the mixture is heated at 100 C. Hexafluoroacetone is slowly admitted until refluxing of it from the condenser causes the temperature to drop. More hexafluoroacetone is added when the original temperature is again attained. 40 parts of hexafluoroacetone are added over a period of 40 hours. Heating is continued for 3 hours at 100 C. Then the reaction mixture is water-washed and the xylene solvent is removed by distillation. 2-('1,1,1,3,3,3-hexafluoro-2- hydroxyisopropyl)-3-methylphenol having a melting point of 81-85" C. is obtained in good yield.

Example 19 Example 18 is repeated except that pentatfluoromonochloroacetone is used instead of hexafluoroacetone and l-butanesulfonic acid (5 parts) is employed as catalyst. A good yield of 2-(1,1,1,3,3-pentafiuoro-3-chloro-2-hydroxyisopropyl)-3-methylphenol is obtained.

Example 20 Example 18 is repeated except that 25 parts of Dowex 50 (acid form) is used as catalyst. A good yield of product is obtained.

Products were also produced employing procedures similar to that described in Example 6 by reacting (1) resorcinol, 1,5-naphthalenediol and p,p'-isopropylidenediphenol with hexafluoroacetone and (2) catechol, resorcinol, Z-phenylphenol, 4-phenylphenol, 4-methylmercaptophenol, 4-nonylphenol, p,p'-isopropylidenediphenol and 2- chlorophenol with sym-tetrafluorodichloroacetone using ptoluenesulfonic acid catalyst.

Infrared spectra for all of the above products showed the presence of fluorine, hydroxy groups and aromatic ring structure.

As indicated above, the compounds of this invention may be employed as active pesticidal toxicants, and particularly as insecticides, miticides and herbicides. The compounds can be employed either as the sole toxicant ingredients, or they can be employed in conjunction with other pesticidally active materials, such as DDT, benzene hexachloride, etc.

The compounds are ordinarily applied as toxicants for combating insects and mites in conjunction with a carrier which may be an inert solid, liquid or gaseous material, or a bait.

When employed in the form of a powder, fine or granular dust for killing insects and mites, the toxicant may be mixed with a substantial proportion of any suitable inert material or diluent, such as known grades of prepared parasiticide carrier clays, pyrophyllite, fullers earth, bentonite, sulfur, lime, talc, whiting, diatomaceous earth, etc. Suitable dusts of this type usually contain not less than 0.5%, and preferably not less than 1% of toxicant.

Liquid insecticide or miticide sprays containing the toxicant may be prepared by first forming a solution of the compound in a suitable organic solvent, e.g. xylene, toluene, or benzene, and preferably adding a small amount of emulsifying agent commonly employed in the art such as diglycol oleate or p-i-sooctyl phenyl ether of polyethylene glycol. The resulting concentrate solution is incorporated with water in amount sufiicient to form an aqueous spray dispersion or emulsion having the desired active ingredient concentration.

In a preferred embodiment, aqueous spray dispersions or suspensions may be formed by incorporating in water so-called dry wettable spray powders or water-dispersible pastes containing the compounds of the invention. These mixtures may also include inert diluents, suitable quantities of wetting, dispersing and suspending agents and, if desired, secondary toxicants.

The aqueous spray dispersions of the invention preferably should contain the toxicant in an amount not less than pound per hundred gallon of spray, the more usual amount being in the range of /2 to 2 pounds per hundred gallons of spray.

The following table shows the results of test on application of typical compounds of this invention to insects and mites. The tests were carried out using 8 pounds or /2 pound of a 25% wettable powder composition per hundred gallons of water. The wettable powder compositions comprised 25% toxicant, 73.5% Attaclay (attapulgite clay carrier), 0.75% Nacconol SW (sodium alkyl aryl sulfonate wetting agent), and 0.75 Elvanol 5105 (polyvinyl alcohol dispersing agent).

Ketone Reactant Aromatic Compound Reactant TABLE Two- Pea Mexican Bean 3outhern Army- Formu- Spotted Aphids, Beetle Larvae, worm Larvae, lation Mites, Percent Percent Kill Percent Kill Percent '11 Kill l-naphthol 2-phenylphenol -methylmercaptophenol 3-isopropylphenol Resorcinol 25% wettable powder composition per hundred gallons of water.

1 of 2 lb. of 25% wettable powder composition per hundred gallons of water.

The tests on toxicity to mites were carried out on twospotted mites (T etranyclzus telarius) by spraying the indicated formulation onto horticultural (cranberry) bean plants infested with the mites. Following treatment, the plants were stored on racks in irrigated trays under greenhouse conditions. Mortality counts were made three days after treatment.

The tests on toxicity to pea aphids (Macrosiphum pisi) were run by removing the pea aphids from infested broad bean plants, placing them on a wire screen and spraying them with the indicated formulation. Following treatment, the pea aphids were confined to untreated broad bean plants. Record of kill was made three days after treatment.

The tests on toxicity to Mexican bean beetle larvae (Epilachna varivestis) and to southern armyworm larvae (Prodenis eridania) were run by spraying horticultural (cranberry) bean plants with the indicated formulation and allowing the plants to dry. The larvae were confined to the treated foliage by means of wire cages. Record of kill was made three days after treatment.

The compounds of this invention are also useful as herbicidal toxicants, particularly in the post-emergent treatment of soil containing noxious broadleaf and grassy weeds.

The toxicants are preferably incorporated in liquid or solid diluents. Compositions similar to the insecticidal and miticidal compositions described above may be employed for herbicidal purposes.

The toxicants are applied to the area to be treated in amount (pounds per acre) sufficient to afford the desired control of vegetation. The optimum intensity of application will depend on such factors as amount of vegetation in the area, degree of permanency of plant eradication desired, type of plants growing in the area and climatic conditions. Hence, as is well known to those skilled in the art, the rate of application actually used will depend largely on prevailing local conditions. In most instances, effective control of germinating weed seeds and small weed seedlings may be realized by applying the toxicant at an overall rate greater than about 2 pounds per acre. Where prolonged control of established vegetation is desired, dosages greater than about 16 pounds per acre are employed.

The following example is illustrative of the postemergent herbicidal activity of the compounds of the present invention. A test plot was covered with rape and ryegrass plants. Each compound was applied by spraying to a designated section of the test plot at the rate of 16 pounds in 40 gallons of acetone per acre, as described by Shaw and Swanson in Weeds, vol. 1, No. 4, pp. 352-365 (July 1952). The following results were obtained several days after treatment:

TABLE Since various modifications may be made without departing from the spirit thereof, the invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. A compound of the formula wherein R is a phenolic radical selected from the group consisting of alkylmercaptophenol in which said alkyl group contains 1 to 9 carbon atoms and alkylenediphenol, said phenolic radical being connected to the adjacent carbon atom at a position ortho to a phenolic hydroxy group, and X and Y are members selected from the group consisting of fluorine and chlorine.

2. A compound as claimed in claim 1 wherein R is a radical of the formula Qt-Q 3. A compound as claimed in claim 1 wherein R is a radical of the formula 4. A process for preparing compounds of the formula R-C(OH) (CF X) (CF Y) wherein R is a nuclearly hydroxy-substituted aryl radical which is selected from the group defined above and has at least one free position which is ortho or para to the hydroxy substituent, with a hexahaloacetone compound of the formula wherein X and Y are fluorine or chlorine.

5. The process of claim 4 wherein the sulfonic acid catalyst is a member selected from the group consisting of (1) alkyl sulfonic acids, (2) aryl sulfonic acids, (3) sulfonic acids formed by adding sulfuric acid to the Kctonc Rcactaut Aromatic Compound Reactant Injury Rating 1 Rape Ryegrass Syin-tctrafluorodichloroacetone Do 3-isopr0pylpl1enol.

Do l-naphthol D0. Z-phenylphenol D0. 4-phenylnhnnnl p,p-isopr0pylidenediphenol 4-methylmcrcapt0pl1enol Do Untreated check Injury Rating0=nonc; 13=s1ight; 4-6=m0derate; 7-9=severo; 10=killed.

9 10 nuclearly hydroxy-substituted aromatic compound, and 3,108,927 10/ 1963 Pyne 167- 31 (4) sulfonic acid form ion-exchange resins. 3,236,894 2/1966 England 260574 6. The process of claim 4 wherein X and Y are fluorine. 7. The process of claim 4 wherein X and Y are chlorine. FOREIGN PATENTS 5 1,325,204 4/ 1963 France. References Cited UNITED STATES PATENTS CHARLES B, PARKER, Primary Examiner.

1,932,886 10 /1933 Dunning 1e7 -70 JULIAN LEVHT Examine" 2,833,830 5/1958 Rigterink 260632 DELBERT R. PHILLIPS, RICHARD HUFF, 2,901,515 8/1959 Rigterink 260632 10 Assislant Examiners.

2,998,348 8/1961 Seydel et a1. 16-731 

1. A COMPOUND OF THE FORMULA
 4. A PROCESS FOR PREPARING COMPOUNDS OF THE FORMULA 